WO2014103623A1 - Polymère à base de fluorène, composé de diol à base de fluorène, et son procédé de production - Google Patents

Polymère à base de fluorène, composé de diol à base de fluorène, et son procédé de production Download PDF

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WO2014103623A1
WO2014103623A1 PCT/JP2013/082423 JP2013082423W WO2014103623A1 WO 2014103623 A1 WO2014103623 A1 WO 2014103623A1 JP 2013082423 W JP2013082423 W JP 2013082423W WO 2014103623 A1 WO2014103623 A1 WO 2014103623A1
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fluorene
group
general formula
compound
acid
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PCT/JP2013/082423
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English (en)
Japanese (ja)
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正晃 松原
俊一 平林
克宏 藤井
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田岡化学工業株式会社
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Priority to CN201380067848.XA priority Critical patent/CN104870517B/zh
Priority to KR1020157018832A priority patent/KR101997314B1/ko
Publication of WO2014103623A1 publication Critical patent/WO2014103623A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation

Definitions

  • the present invention relates to a fluorene polymer that can be suitably used as a resin (optical resin) constituting an optical member typified by an optical lens or an optical film. Moreover, this invention relates to the fluorene type diol compound suitable as a monomer which forms the said fluorene type polymer, and its manufacturing method.
  • Polycarbonate resin, cycloolefin resin, polymethacrylic resin, and the like have been conventionally used as optical resins because they are relatively excellent in high refractive index properties, low birefringence properties, transparency, and processability.
  • a skeleton of a so-called “cardo structure” in which two phenyl groups are introduced at the 9-position of fluorene since it is particularly advantageous for achieving both high refractive index and low birefringence, a skeleton of a so-called “cardo structure” in which two phenyl groups are introduced at the 9-position of fluorene.
  • An optical resin made of a fluorene-based polymer has attracted attention, and active research and development has been conducted.
  • Patent Document 1 discloses a polycarbonate resin having 9,9-bis (4-hydroxyphenyl) fluorenes as a part of the diol component.
  • Patent Document 2 discloses a polyester polymer for an optical material having 9,9-bis (4-hydroxyalkoxyphenyl) fluorene as a part of a diol component.
  • Patent No. 5011450 discloses a polyester carbonate copolymer for optical lenses having 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component. Yes.
  • the present invention includes the following. [1] The following general formula (I):
  • R 1 represents an alkyl group, a cycloalkyl group or an aryl group.
  • R 2 represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 1 to 5.
  • R 1 represents an alkyl group, a cycloalkyl group or an aryl group.
  • R 1 represents an alkyl group, a cycloalkyl group or an aryl group.
  • the fluorene polymer according to the present invention containing the structural unit derived from the fluorene diol compound represented by the above general formula (I) has both high refractive index and low birefringence, transparency and heat resistance. And is suitable as an optical resin constituting an optical member such as an optical lens, an optical film, a plastic optical fiber, and an optical disk substrate. Further, taking advantage of its high heat resistance, transparency, durability, etc., it can also be used as a non-optical resin such as a heat resistant resin or engineering plastic.
  • the present invention it is possible to provide a fluorene-based diol compound represented by the above general formula (I) that is useful as a raw material monomer for the fluorene-based polymer.
  • the compound represented by the above general formula (III) can be produced with high reaction selectivity, so that the fluorene-based diol compound represented by the general formula (I) having high purity can be collected. It can be obtained efficiently.
  • the fluorene polymer of the present invention (hereinafter also simply referred to as “fluorene polymer”) is a polymer containing a structural unit derived from the fluorene diol compound represented by the general formula (I) in the main chain.
  • R 1 is an alkyl group, a cycloalkyl group or an aryl group.
  • R 2 represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 1 to 5.
  • Examples of the alkyl group in R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, and a hexyl group.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably 1 to 8 carbon atoms. 3 linear or branched alkyl groups.
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, alkyl having 1 to 4 carbons) substituted cyclopentyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted cyclohexyl group, and the like. And a cycloalkyl group having 16 to 16 (preferably 5 to 8 carbon atoms) or an alkyl-substituted cycloalkyl group.
  • the cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group.
  • aryl group examples include a phenyl group, an alkyl (for example, alkyl having 1 to 4 carbon atoms) -substituted phenyl group, and a naphthyl group.
  • the aryl group is preferably a phenyl group or an alkyl-substituted phenyl group (for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, etc.), and more preferably a phenyl group.
  • the alkyl group, cycloalkyl group, and aryl group may have a substituent other than the alkyl group (for example, an alkoxyl group, an acyl group, a halogen atom, etc.).
  • the alkylene group represented by R 2 can be linear or branched, and examples thereof include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
  • the alkylene group represented by R 2 is preferably a linear or branched alkylene group having 2 to 4 carbon atoms, and more preferably a linear or branched alkylene group having 2 or 3 carbon atoms.
  • N representing the number of repetitions of OR 2 is preferably 1 to 3, more preferably 1 or 2, and typically 1.
  • (OR 2 ) n may be composed of the same OR 2 or may be composed of two or more different OR 2 . Further, the two (OR 2 ) n OH groups possessed by the fluorene-based diol compound represented by the general formula (I) can have different repeating numbers n.
  • the fluorene polymer may be a thermoplastic resin such as a polycarbonate resin, a polyester resin, a polyester carbonate resin, a (meth) acrylic resin, a polyurethane resin, or a heat such as an epoxy resin, a (meth) acrylic resin, or a polyurethane resin.
  • a curable resin or a photocurable resin it is preferably a thermoplastic resin that can be injection-molded when a molded article such as an optical member is produced.
  • the fluorene-based polymer of the present invention includes modified products of various resins as described above. Examples of the modified product include those having a functional group or molecular chain introduced at the end of the polymer, and those having a functional group or molecular chain introduced as a side chain of the polymer.
  • the fluorene-based polymer exhibits a very high refractive index while exhibiting a low birefringence due to including a structural unit derived from the fluorene-based diol compound represented by the general formula (I).
  • the refractive index (23 ° C.) is the type of polymer, the chemical structure of the constituent units constituting the polymer, the presence / absence of constituent units derived from other diol components other than the fluorene diol compound, the content rate and / or Although it may vary depending on the chemical structure (type of other diol component) and the like, it is typically 1.6 or more.
  • the fluorene-based polymer may exhibit a refractive index of 1.61 or more, further 1.62 or more, and even more 1.64 or more.
  • the refractive index (20 ° C.) of a general polycarbonate resin for example, bisphenol A or the like is used as a diol component
  • a cycloolefin resin or a polymethacrylic resin that is widely used as an optical resin
  • the fluorene polymer of the present invention is extremely superior in terms of refractive index as compared with these general conventional general-purpose optical resins.
  • polyester resin containing 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component and is a conventionally known fluorene heavy polymer as a high refractive index optical resin.
  • fluorene polymer a polyester resin containing 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component and is a conventionally known fluorene heavy polymer as a high refractive index optical resin.
  • the refractive index (20 ° C.) of these polyester resins is about 1.60 to about 1.63.
  • the fluorene polymer of the present invention containing a structural unit derived from the fluorene-based diol compound represented by the above general formula (I) is superior in terms of refractive index as compared with the above-mentioned conventionally known fluorene-based polymer. It can be said that. Such an improvement in refractive index is presumed to be due to the difference in the positions of the (OR 2 ) n OH groups on the two phenyl groups.
  • the fluorene polymer of the present invention has a “cardo structure” (a fluorene ring, which is a structural unit derived from a fluorene diol compound) and two bonded to the 9-position thereof.
  • Low birefringence is realized by a structure comprising a phenyl group).
  • a polymer for example, a polymer containing 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component.
  • a polymer for example, a polymer containing 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component.
  • the fluorene polymer of the present invention is a material suitable as an optical resin even in terms of a low Abbe number.
  • the fluorene-based polymer can exhibit a low Abbe number of 30 or less, further 27 or less, and even 24 or less at 23 ° C., and can also exhibit an Abbe number of 22 or less.
  • the Abbe numbers (20 ° C.) of the trade names “OKP4” and “OKP4HT” manufactured by Osaka Gas Chemical Co., Ltd. are 27 and 23, respectively.
  • the fluorene polymer of the present invention has sufficient heat resistance as an optical resin. That is, the fluorene polymer of the present invention typically has a glass transition temperature of about 130 ° C. or higher, and has a glass transition temperature of 140 ° C. or higher, further 150 ° C. or higher, and even more preferably 155 ° C. or higher. May also have.
  • the glass transition temperatures of general polycarbonate resins, cycloolefin resins, and polymethacrylic resins that are widely used as optical resins are about 145 ° C., about 140 ° C., and about 110 ° C., respectively, and 9,9-bis [4
  • the glass transition temperature of the polyester resin having a diol component of (2-hydroxyethoxy) phenyl] fluorene (for example, trade names “OKP4” and “OKP4HT” manufactured by Osaka Gas Chemical Co., Ltd.) and polycarbonate resin is about 120 respectively. 140 ° C. and about 150 ° C. (when the diol component consists only of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene).
  • the fluorene polymer of the present invention also has sufficient transparency, workability (moldability, etc.) and durability required for optical resins.
  • the fluorene polymer of the present invention which is a polycarbonate resin, reacts a diol component containing the fluorene diol compound represented by the general formula (I) with a carbonic acid diester or phosgene in the presence or absence of a polymerization catalyst. It can be obtained according to conventional methods.
  • the polycarbonate resin of the present invention is a resin containing a carbonate bond in which the OH group of the (OR 2 ) n OH group represented by the general formula (I) is involved in the main chain. -1):
  • the diol component is only one kind of fluorene-based diol compound represented by the general formula (I) (for example, a compound in which R 1 in the general formula (I) is a methyl group or an ethyl group, and an (OR 2 ) n OH group A compound that is a specific one) or two or more (that is, a plurality of compounds in which R 1 , R 2, and / or n in general formula (I) are different from each other). Also good.
  • the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I). Other diol components may be used alone or in combination of two or more.
  • diol components include fluorene diol compounds other than the fluorene diol compound represented by the general formula (I) [for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-alkyl-substituted phenyl) fluorene and their alkylene oxides (eg, alkylene oxides having 2 to 6 carbon atoms) adducts, etc.]; alkylene glycols [for example, ethylene glycol, propylene glycol, trimethylene glycol, 1, 3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, linear or branched alkylene glycol having 2 to 12 carbon atoms represented by decanediol, etc.]; (poly) oxyalkylene glycol [for example The Di-, tri- or tetra-alkylene glycol
  • a tri- or higher functional polyol component such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination.
  • carbonic acid diester examples include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate.
  • Carbonic acid diester can be used individually or in combination of 2 or more types.
  • polymerization catalysts include, for example, alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (zinc, aluminum, germanium, tin, lead, antimony, titanium) , Manganese, cobalt, lancerium, etc.].
  • the metal compound include hydroxides, alcoholates, organic acid salts (acetates, propionates, etc.), inorganic acid salts (borate, carbonates, etc.), oxides, and the like.
  • a polymerization catalyst can be used individually or in combination of 2 or more types.
  • the molecular weight of the polycarbonate resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 100,000 in terms of weight average molecular weight (polystyrene conversion).
  • the fluorene polymer of the present invention which is a polyester resin, is a conventional reaction in which a diol component containing a fluorene diol compound represented by the above general formula (I) and a dicarboxylic acid component are reacted in the presence or absence of a polymerization catalyst. It can be obtained according to a method [for example, direct polymerization method (direct esterification method) or transesterification method].
  • the polyester resin of the present invention is a resin containing an ester bond in which the OH group of the (OR 2 ) n OH group represented by the general formula (I) is involved in the main chain. -2):
  • R 1 , R 2 and n in the formula are as described above.
  • Q is a divalent residue excluding the carboxyl group of the dicarboxylic acid component (or a derivative group capable of forming an ester thereof).
  • the diol component may contain only one kind of fluorene diol compound represented by the general formula (I), or may contain two or more kinds. Moreover, the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I). Other diol components may be used alone or in combination of two or more. Specific examples of other diol components and the content ratio of the fluorene-based diol compound represented by the general formula (I) to the other diol components in the diol component can be the same as those described for the polycarbonate resin.
  • a tri- or higher functional polyol component such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination.
  • dicarboxylic acid component examples include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives capable of forming esters thereof (for example, acid anhydrides, acid chlorides, lower alkyl esters, etc.).
  • a dicarboxylic acid component can be used individually or in combination of 2 or more types.
  • aliphatic dicarboxylic acid examples include saturated aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, etc.
  • saturated aliphatic dicarboxylic acids for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, etc.
  • Unsaturated aliphatic dicarboxylic acids eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.
  • alicyclic dicarboxylic acid examples include saturated alicyclic dicarboxylic acids [for example, cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane.
  • Dicarboxylic acid etc. unsaturated alicyclic dicarboxylic acid [eg 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid etc.]; polycyclic alkane dicarboxylic acid [eg bornane dicarboxylic acid, norbornane dicarboxylic acid , Adamantane dicarboxylic acid, etc.]; polycyclic alkene dicarboxylic acids [for example, bornene dicarboxylic acid, norbornene dicarboxylic acid, etc.]; and their ester-forming derivatives.
  • unsaturated alicyclic dicarboxylic acid eg 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid etc.
  • polycyclic alkane dicarboxylic acid eg bornane dicarboxylic acid, norbornane dicarboxylic acid , Adamantane di
  • aromatic dicarboxylic acid examples include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4′-diphenyldicarboxylic acid, diphenylether-4,4′-dicarboxylic acid. 4,4′-diphenylmethane dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, and their ester-forming derivatives.
  • a tri- or higher functional carboxylic acid component such as trimellitic acid or pyromellitic acid may be used in combination with the dicarboxylic acid component.
  • the same ones as described for the polycarbonate resin can be used.
  • the molecular weight of the polyester resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 100,000 in terms of weight average molecular weight (polystyrene conversion).
  • the fluorene polymer of the present invention which is a polyester carbonate resin comprises a diol component containing a fluorene diol compound represented by the above general formula (I), a carbonic acid diester or phosgene, and a dicarboxylic acid component in the presence of a polymerization catalyst or It can be obtained according to a conventional method of reacting in the absence.
  • the polyester carbonate resin of the present invention is a resin comprising a carbonate bond involving the OH group of the (OR 2 ) n OH group represented by the general formula (I) and an ester bond involving the OH group in the main chain. Specifically, it is a resin containing the structural units represented by the general formula (I-1) and the general formula (I-2) in the main chain.
  • the diol component may contain only one kind of fluorene diol compound represented by the general formula (I), or may contain two or more kinds. Moreover, the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I).
  • the other diol component, carbonic acid diester and dicarboxylic acid component can be used alone or in combination of two or more. Specific examples of other diol components, carbonic acid diesters and dicarboxylic acid components, and the content ratio of the fluorene-based diol compound represented by the general formula (I) in the diol component to other diol components are described for polycarbonate resins and polyester resins. Can be similar to
  • a tri- or higher functional polyol component such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination.
  • the molecular weight of the polyester carbonate resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 100,000 in terms of weight average molecular weight (polystyrene conversion).
  • the fluorene polymer of the present invention which is a polyurethane resin, is a conventional method in which a diol component containing a fluorene diol compound represented by the above general formula (I) and a diisocyanate component are urethanated in the presence or absence of a polymerization catalyst. Can be obtained according to the method.
  • the diol component may contain only one kind of fluorene diol compound represented by the general formula (I), or may contain two or more kinds. Moreover, the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I). Other diol components may be used alone or in combination of two or more. Specific examples of other diol components and the content ratio of the fluorene-based diol compound represented by the general formula (I) to the other diol components in the diol component can be the same as those described for the polycarbonate resin.
  • a tri- or higher functional polyol component such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination.
  • diisocyanate component examples include aromatic diisocyanates [for example, paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis (isocyanato Phenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis (isocyanatophenyl) propane, 1,4-bis (isocyanatophenyl) butane, polymeric MDI, etc.]; Alicyclic diisocyanates [eg, cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.]; Aliphatic diisocyanates Pre
  • the amount of the diisocyanate component used in the urethanization reaction is usually about 0.7 to 2.5 mol, preferably about 0.8 to 2.2 mol, relative to 1 mol of the diol component.
  • a polymerization catalyst well-known urethanation catalysts, such as an amine type, a tin type, and a lead type, can be used, for example.
  • the fluorene polymer (resin) of the present invention may be used alone as a material for a resin member such as an optical member [for example, an optical lens, an optical film], or combined with other components to form a resin composition. This may be used as a material for the resin member.
  • the resin composition can contain a resin other than the fluorene polymer of the present invention, and can contain an appropriate additive as required. Specific examples of additives include plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, fillers, flame retardants, colorants, dispersants, flow agents Contains modifiers, leveling agents, antifoaming agents, etc.
  • An additive can be used individually or in combination of 2 or more types.
  • the fluorene polymer (resin) of the present invention or a resin composition containing the same is, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, etc. It can shape
  • fluorene-based diol compound represented by the above general formula (I) (hereinafter also simply referred to as “fluorene-based diol compound”) is a compound suitably used as a raw material monomer for forming the above-mentioned fluorene polymer. It is.
  • R 1 is an alkyl group, a cycloalkyl group or an aryl group. Specific examples of the alkyl group, cycloalkyl group and aryl group are as described above.
  • R 2 represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 1 to 5.
  • the alkylene group represented by R 2 can be linear or branched, and examples thereof include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. It is done.
  • the alkylene group represented by R 2 is preferably a linear or branched alkylene group having 2 to 4 carbon atoms, and more preferably a linear or branched alkylene group having 2 or 3 carbon atoms.
  • n representing the number of repetitions of OR 2 is preferably 1 to 3, more preferably 1 or 2, and typically 1.
  • (OR 2 ) n may be composed of the same OR 2 or may be composed of two or more different OR 2 .
  • the two (OR 2 ) n OH groups possessed by the fluorene-based diol compound may have different repeating numbers n.
  • the refractive index (23 ° C.) of the fluorene-based diol compound is, for example, about 1.60 to 1.61 when R 1 is a methyl group or an ethyl group and the two (OR 2 ) n OH groups are hydroxyethoxy groups. It is.
  • This refractive index value is the refractive index value of 1.9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, which is a raw material monomer of a fluorene polymer that has been conventionally known to exhibit a high refractive index. 62.
  • the fluorene-based diol compound itself has a low Abbe number, and can exhibit a low Abbe number of 30 or less, further 27 or less, and even 25 or less at 23 ° C.
  • a fluorene-based bisphenol compound represented by the following general formula (III) (hereinafter referred to as “compound”) is subjected to a condensation reaction between 9-fluorenone and m-alkylphenol represented by the above general formula (II) under acidic conditions. (III) "), and (B) a step of converting the OH group of compound (III) into an (OR 2 ) n OH group.
  • R 1 in the general formulas (II) and (III) is the same as in the general formula (I).
  • the meanings of R 2 and n in the (OR 2 ) n OH group formed in the step (B) are also as described above.
  • the fluorene diol compound according to the present invention is an alkylene oxide adduct of compound (III).
  • step (A) a method of performing the above condensation reaction in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound can be mentioned.
  • compound (III) can be formed with high reaction selectivity, and a high-purity fluorene-based diol compound represented by general formula (I) can be obtained in high yield.
  • m-alkylphenol is usually used in an excess amount relative to 9-fluorenone.
  • the ratio of the amount of m-alkylphenol used relative to the amount of 9-fluorenone used is usually 2.0 to 40 times (eg, 2.1 to 40 times), preferably 3 to 30 times, more preferably, molar ratio. 4 to 20 times.
  • the condensation reaction can be carried out in the presence or absence of a solvent, and an excess amount of m-alkylphenol is also preferably used as the solvent.
  • organic acid paratoluenesulfonic acid, methanesulfonic acid, or the like can be used.
  • inorganic acid hydrohalic acid such as hydrochloric acid (hydrogen chloride aqueous solution), phosphoric acid, or the like can be used.
  • the hydrogen chloride concentration of hydrochloric acid is preferably 10 to 37% by weight, more preferably 20 to 37% by weight, and still more preferably 25 to 37% by weight.
  • paratoluenesulfonic acid, hydrochloric acid (especially high-concentration hydrochloric acid) or the like because high reaction selectivity and thus high yield can be obtained.
  • the acidic compound (organic acid and / or inorganic acid) can be used alone or in combination of two or more.
  • a xanthene compound represented by the formula (1) is produced as a main reaction product, and the use of sulfuric acid (concentrated sulfuric acid) is relatively disadvantageous in this respect.
  • sulfuric acid concentrated sulfuric acid
  • hydrochloric acid especially high concentration hydrochloric acid
  • the ratio of the amount of acidic compound (organic acid or inorganic acid) used relative to the amount of 9-fluorenone used (in the case of a solution such as hydrochloric acid, the amount of acidic compound contained in the solution) is usually 0.05. -3 times, preferably 0.1-2 times, more preferably 0.2-1.5 times.
  • thiol compound examples include alkyl mercaptans [eg, alkyl mercaptans having 1 to 20 carbon atoms such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, n-lauryl mercaptan]; aralkyl mercaptans [eg, benzyl mercaptan Etc.]; mercaptocarboxylic acids (eg, thioacetic acid, ⁇ -mercaptopropionic acid, ⁇ -mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.); and salts thereof (eg, Na Salt, K salt, etc.] can be used.
  • a thiol compound can be used individually or in combination of 2 or more types.
  • the ratio of the amount of the thiol compound used relative to the amount of 9-fluorenone used is usually 0.01 to 0.5 times, preferably 0.02 to 0.3 times, more preferably 0.03 to 0.3 in terms of molar ratio. 0.2 times.
  • condensation reaction is carried out in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound, for example, the starting materials 9-fluorenone and m-alkylphenol, acidic compound, thiol compound, Moreover, it can carry out by charging the solvent used as needed to reaction container, and stirring in air or inert gas atmosphere, such as nitrogen and helium.
  • Liquid containing an acidic compound for example, liquid acid itself (hydrochloric acid hydrochloric acid itself), solid acid dissolved in a solvent), or liquid containing an acidic compound and a thiol compound It is also effective to add the solution to a reaction vessel charged with another reagent while stirring.
  • the reaction temperature is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 15 ° C. or higher from the viewpoint of the reaction rate.
  • the reaction temperature is preferably 60 ° C or lower, more preferably 50 ° C or lower, and 40 ° C or lower. More preferably, it is particularly preferably 35 ° C. or lower.
  • HPLC high performance liquid chromatography
  • the compound (III) can be isolated as crystals by performing an appropriate post-treatment operation.
  • the post-treatment operations include extraction of compound (III) into an organic layer (organic solvent), neutralization of an acidic compound with alkali, washing of the organic layer, concentration of the organic layer, crystallization, filtration, and drying. One or more of these operations may be omitted, or other operations may be added.
  • the purification method include recrystallization (recrystallization) and impurity removal treatment using an adsorbent such as activated carbon.
  • the compound (III) produced by the condensation reaction in the step (A) may be subjected to the next step (B) without being isolated as crystals.
  • Conversion of the OH group to the (OR 2 ) n OH group in the step (B) is carried out by converting the compound (III) and the alkylene oxide corresponding to the desired (OR 2 ) n OH group [for example, ethylene oxide, propylene oxide, etc.] Alternatively, it can be carried out according to a conventional method in which an alkylene carbonate [for example, ethylene carbonate, propylene carbonate, etc.] is reacted in the presence or absence of a catalyst [base catalyst, etc.]. The progress of the reaction can be monitored by high performance liquid chromatography (HPLC) or the like.
  • HPLC high performance liquid chromatography
  • the fluorene diol compound represented by the general formula (I) can be isolated as crystals by performing an appropriate post-treatment operation.
  • the post-treatment operation include extraction of a fluorene-based diol compound into an organic layer (organic solvent), washing of the organic layer, concentration of the organic layer, crystallization, filtration, and drying.
  • One or more operations may be omitted or other operations may be added.
  • the purification method include recrystallization (recrystallization) and impurity removal treatment using an adsorbent such as activated carbon. You may use for the manufacturing process of the above-mentioned fluorene type polymer, without isolating the fluorene type diol compound produced
  • a fluorene diol compound can also be produced by a method including the following steps.
  • alkylene oxide adduct (V) condensing 9-fluorenone and the alkylene oxide adduct (V) under acidic conditions, and obtaining the alkylene oxide adduct represented by the formula (hereinafter also referred to as “alkylene oxide adduct (V)”). Reacting.
  • alkylene oxide adduct (V) examples include (3-methylphenoxy) ethanol, (3-ethylphenoxy) ethanol, (3-methylphenoxy) propanol, (3-ethylphenoxy) propanol, (3-methylphenoxy) butanol, And (3-ethylphenoxy) butanol.
  • Process (a) and (b) can be performed similarly to the above-mentioned process (B) and (A), respectively.
  • HPLC purity The area percentage value when HPLC measurement was performed under the following measurement conditions was defined as HPLC purity.
  • Weight average molecular weight of fluorene polymer The weight average molecular weight was measured (polystyrene conversion) using a high-speed GPC apparatus ("HLC-8200 GPC" manufactured by Tosoh Corporation).
  • Haze of fluorene polymer Haze was measured using a haze meter (“HGM-2DP” manufactured by Suga Test Instruments Co., Ltd.).
  • the precipitated crystals are filtered and dried, and white crystals of the fluorene diol compound IIIb [9,9-bis (2-hydroxy-4-methylphenyl) fluorene] in which R 1 in the above general formula (III) is a methyl group 48.1 g was obtained (9-fluorenone based yield: 57.3%).
  • the HPLC purity of the white crystals was 90.3%.
  • FIGS. 1 and 2 show HH COSY and CH COSY spectra of the fluorene diol compound Ia, respectively.
  • FIGS. 3 and 4 show HH COSY and CH COSY spectra of the fluorene diol compound Ib, respectively. Shown in From these two-dimensional NMR spectra, the fluorene-based diol compounds Ia and Ib have a structure as shown by the above general formula (I), and in particular, the (OR 2 ) n OH group is the 2-position of the phenyl group. It was confirmed that R 1 was bonded to the 4-position.
  • the temperature was raised to 210 ° C. at a rate of 60 ° C./hr, and the mixture was stirred at the same temperature for 30 minutes. Then, it heated up to 220 degreeC at the speed
  • reaction container was made into 133 Pa or less over 1 hour, and it stirred for 10 minutes on 240 degreeC and 133 Pa or less conditions, and was complete
  • Example 4 Production of polycarbonate resin> Fluorene-based diol compound Ib [9,9-bis [2- (2-hydroxyethoxy) -4-methylphenyl] fluorene] 18.09 parts by weight, diphenyl carbonate 8.60 parts by weight and sodium hydrogen carbonate 2 as a polymerization catalyst 0.0 ⁇ 10 ⁇ 5 parts by weight was charged into a reaction vessel equipped with a stirrer and a distillation apparatus, heated to 200 ° C. in a nitrogen atmosphere, and stirred for 20 minutes to be completely melted. Then, the pressure reduction degree in reaction container was adjusted to 27 kPa, and it stirred for 30 minutes on 200 degreeC and 27 kPa conditions. Next, the temperature was raised to 210 ° C.
  • reaction container was made into 133 Pa or less over 1 hour, and it stirred for 10 minutes on 240 degreeC and 133 Pa or less conditions, and was complete
  • reaction container was made into 133 Pa or less over 1 hour, and it stirred on 240 degreeC and 133 Pa or less conditions for 1 hour, and was complete

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne : un polymère à base de fluorène qui contient un motif constitutif dérivé d'un composé de diol à base de fluorène représenté par la formule générale (I) dans sa chaîne principale ; le composé de diol à base de fluorène ; et un procédé de production dudit composé de diol à base de fluorène. (Dans la formule, R1 représente un groupe alkyle, un groupe cycloalkyle ou un groupe aryle ; R2 représente un groupe alkylène ayant de 2 à 6 atomes de carbone ; et n représente un entier de 1 à 5).
PCT/JP2013/082423 2012-12-25 2013-12-03 Polymère à base de fluorène, composé de diol à base de fluorène, et son procédé de production WO2014103623A1 (fr)

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JP2011074222A (ja) * 2009-09-30 2011-04-14 Osaka Gas Co Ltd フルオレン骨格を有するポリエステル樹脂
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JP2843215B2 (ja) 1992-07-30 1999-01-06 鐘紡株式会社 ポリエステル重合体およびその成形体並びに成形体の製造方法
WO1999019771A1 (fr) * 1997-10-13 1999-04-22 Pi R & D Co., Ltd. Composition de polyimide photosensible positive
WO2010119727A1 (fr) * 2009-04-13 2010-10-21 田岡化学工業株式会社 Procédé pour produire un dérivé de fluorène
JP2012224759A (ja) * 2011-04-20 2012-11-15 Teijin Chem Ltd ３ｄ液晶表示の前面板用シート
JP6139508B2 (ja) * 2012-03-09 2017-05-31 本州化学工業株式会社 ９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレンの製造方法、その結晶体、及びその結晶体の製造方法

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JP2002047227A (ja) * 2002-01-29 2002-02-12 Osaka Gas Co Ltd フルオレン誘導体の製造方法
JP2009155251A (ja) * 2007-12-26 2009-07-16 Osaka Gas Co Ltd フルオレン骨格を有するアルコール
JP2011074222A (ja) * 2009-09-30 2011-04-14 Osaka Gas Co Ltd フルオレン骨格を有するポリエステル樹脂
JP2011236336A (ja) * 2010-05-11 2011-11-24 Teijin Chem Ltd 光弾性定数が低いポリカーボネート樹脂および光学成形体

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